This study reports the development of a two-dimensional coupled hybrid catalyst for efficient hydrogen evolution reaction (HER). The catalyst, composed of molybdenum carbide (Mo2C) encapsulated by nitrogen and phosphorus-doped carbon shells and nitrogen, phosphorus-doped reduced graphene oxide (NPRGO), is synthesized using a PMo12–polypyrrole/reduced graphene oxide (PPy/RGO) nanocomposite as a precursor. The hybrid catalyst exhibits superior electrocatalytic activity for HER, with a low onset overpotential of 0 mV, a small Tafel slope of 33.6 mV dec−1, and excellent stability in acidic media. Theoretical calculations reveal that the active sites for HER are primarily composed of pyridinic nitrogen and carbon atoms in the graphene. This work opens new avenues for the design of nanomaterials for HER applications.This study reports the development of a two-dimensional coupled hybrid catalyst for efficient hydrogen evolution reaction (HER). The catalyst, composed of molybdenum carbide (Mo2C) encapsulated by nitrogen and phosphorus-doped carbon shells and nitrogen, phosphorus-doped reduced graphene oxide (NPRGO), is synthesized using a PMo12–polypyrrole/reduced graphene oxide (PPy/RGO) nanocomposite as a precursor. The hybrid catalyst exhibits superior electrocatalytic activity for HER, with a low onset overpotential of 0 mV, a small Tafel slope of 33.6 mV dec−1, and excellent stability in acidic media. Theoretical calculations reveal that the active sites for HER are primarily composed of pyridinic nitrogen and carbon atoms in the graphene. This work opens new avenues for the design of nanomaterials for HER applications.